US10892242B2 - Resin composition, conductive copper paste, and semiconductor device - Google Patents

Resin composition, conductive copper paste, and semiconductor device Download PDF

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US10892242B2
US10892242B2 US16/067,873 US201716067873A US10892242B2 US 10892242 B2 US10892242 B2 US 10892242B2 US 201716067873 A US201716067873 A US 201716067873A US 10892242 B2 US10892242 B2 US 10892242B2
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resin composition
component
resin
acid
curing
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Tomoyuki Takahashi
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Namics Corp
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Namics Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29199—Material of the matrix
    • H01L2224/2929—Material of the matrix with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29199—Material of the matrix
    • H01L2224/29294—Material of the matrix with a principal constituent of the material being a liquid not provided for in groups H01L2224/292 - H01L2224/29291
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29347—Copper [Cu] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29499—Shape or distribution of the fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/32227—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation the layer connector connecting to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/83855—Hardening the adhesive by curing, i.e. thermosetting
    • H01L2224/83862—Heat curing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector

Definitions

  • the present invention relates to a resin composition, a conductive copper paste, and a semiconductor device.
  • the present invention relates to a resin composition, a conductive copper paste, and a semiconductor device, which have low specific resistance.
  • a semiconductor device in which the electrode portion of a semiconductor element and the conductive portion of a substrate are bonded to each other is very extensively used.
  • a conductive adhesive or soldering is used for bonding the electrode portion of a semiconductor element and the conductive portion of a substrate.
  • the conductive adhesive has the advantage that bonding can be performed at a lower temperature than soldering.
  • the specific resistance of the conductive adhesive is higher than that of solder. Therefore, studies are underway to reduce the resistance of the conductive adhesive.
  • Known conductive adhesives include silver as a conductive filler.
  • silver has migration properties and has increased in price, studies are underway to use copper as a conductive filler.
  • the conductive adhesive including copper generally has the drawback that the specific resistance is high.
  • a conductive copper paste containing as essential components a copper powder having a predetermined particle size distribution and tap density, a thermosetting resin, an organic carboxylic acid, and a chelate agent, and furthermore, polybutadiene (claim 1 and paragraphs 0013 and 0022 of PATENT LITERATURE 1).
  • This conductive copper paste is prepared such that it is a conductive copper paste which enables screen printing, has favorable conductivity comparable to a conductive silver paste, and possesses migration resistance properties, and which is suitable for through holes corresponding to fine pitches (paragraph 0008 of PATENT LITERATURE 1).
  • specific examples of the organic carboxylic acid may include salicylic acid, benzoic acid, tartaric acid, citric acid, maleic acid, succinic acid, fumaric acid, and malonic acid (paragraph 0018 of PATENT LITERATURE 1). All these organic carboxylic acids are solid at normal temperature.
  • this conductive paste for circuit boards may include a compound having flux activity (paragraph 0014 of PATENT LITERATURE 2).
  • An example of the compound having flux activity may include aliphatic carboxylic acids such as oleic acid (paragraphs 0038 and 0046 of PATENT LITERATURE 2).
  • a conductive copper paste composition which includes a prepolymer having at least two hydroxyl groups and at least one tertiary amine in one molecule, a copper powder, an amino resin, and a reducing agent, and which can be etched by an acidic etchant (claim 1 of PATENT LITERATURE 3).
  • the reducing agent may include an unsaturated monocarboxylic acid having 12 to 23 carbon atoms, such as oleic acid and linoleic acid (paragraph 0016 of PATENT LITERATURE 3).
  • these conductive copper pastes have the following problems. That is, the specific resistance of the conductive copper pastes is likely to become high, and furthermore, significantly changes after curing depending on the content of a copper powder.
  • usable resins are substantially limited (a resol-type phenolic resin according to PATENT LITERATURE 1, a compound having at least two (meth)acryl groups in one molecular according to PATENT LITERATURE 2, and a prepolymer having at least two hydroxyl groups and at least one tertiary amine in one molecule and an amino resin according to PATENT LITERATURE 3), applicable uses are limited.
  • an object of the present invention is to provide: a resin composition in which the specific resistance after curing is low regardless of the type of a thermosetting resin and does not significantly change depending on the content of a copper powder; and a conductive copper paste including the resin composition.
  • the present invention relates to a resin composition, a conductive copper paste, a cured product of a conductive copper paste, and a semiconductor device, which have solved the above-described problems by having the following configurations.
  • a resin composition including (A) a copper powder having an oxygen content of 0.3% by mass or less, (B) a thermosetting resin, (C) a fatty acid, and (D) an amine or an amine compound.
  • a semiconductor device including a cured product of the resin composition according to the above-described ⁇ 1>.
  • thermosetting resin in which the specific resistance is low after curing regardless of the type of the thermosetting resin and does not significantly change after curing depending on the content of the copper powder (the specific resistance value is less than 1 ⁇ 10 ⁇ 4 ⁇ cm).
  • a conductive copper paste including the resin composition in which the specific resistance is low after curing regardless of the type of the thermosetting resin and does not significantly change after curing depending on the content of the copper powder (the specific resistance value is less than 1 ⁇ 10 ⁇ 4 ⁇ cm).
  • a cured product of a low-resistance conductive copper paste for obtaining a highly reliable semiconductor device.
  • a highly reliable semiconductor device which, for example, has a small connection resistance value between the electrode portion of a semiconductor element and the conductive portion of a substrate.
  • the resin composition according to the present invention includes (A) a copper powder having an oxygen content of 0.3% by mass or less, (B) a thermosetting resin, (C) a fatty acid, and (D) an amine or an amine compound.
  • the copper powder having an oxygen content of 0.3% by mass or less relative to 100% of the copper powder as the (A) component imparts conductivity to the resin composition after curing.
  • the resin composition is advantageous in that the specific resistance after curing does not significantly change depending on the content of the (A) component.
  • the oxygen content of the copper powder is measured by hydrogen loss method. Specifically, an oxygen-nitrogen analyzer (Model: EMGA-623W) manufactured by Horiba, Ltd. is used for the measurement. It is noted that the oxygen content of the copper powder in the resin composition is measured after the copper powder is retrieved from the resin composition by solvent.
  • the (A) component preferably has an average particle size of 1 to 10 ⁇ m, from the viewpoint of the oxygen content and the specific resistance of the resin composition after curing.
  • An example of the (A) component may include a copper powder having a rod-like, flake-like, or spherical shape.
  • a more preferable example of the (A) component may be a rod-like copper powder obtained by crushing a particle-shaped dendritic copper powder (electrolytic copper powder).
  • the tap density of the (A) component is high from the viewpoint of the specific resistance of the resin composition after curing.
  • Examples of a commercially available product of the (A) component may include: an electrolytic copper powder manufactured by Mitsui Mining & Smelting Co., Ltd.
  • the (A) component may be used alone. Alternatively, two or more of the (A) components may be used in combination.
  • the thermosetting resin as the (B) component imparts adhesiveness and curing properties to the resin composition.
  • the (B) component is preferably, but not particularly limited to, at least one selected from the group consisting of an epoxy resin, a phenolic resin, a melamine resin, a xylene resin, and a urea resin, from the viewpoint of adhesive strength.
  • Examples of a commercially available product of the (B) component may include: a bisphenol F-type epoxy resin manufactured by DIC Corporation (product name: EPICLON EXA-835LV); a bisphenol A-type epoxy resin manufactured by Asahi Kasei E-materials Corporation (product name: AER6072); a Novolac-type phenolic resin manufactured by Meiwa Plastic Industries, Ltd. (product name: MEH-8005); a Novolac-type phenolic resin manufactured by Gun Ei Chemical Industry Co., Ltd. (product name: Resitop PSM4324); a resol-type phenolic resin manufactured by Showa Highpolymer Co., Ltd.
  • the (B) component may be used alone. Alternatively, two or more of the (B) components may be used in combination. It is noted that solid resin such as a resol-type phenolic resin may be heated and mixed with the later-described diluent when preparing a paste so that it is used in a liquid state.
  • the (C) component functions as a flux component which allows an oxidized layer on the surface of the copper powder to be eluted.
  • the (C) component is preferably at least one selected from the group consisting of
  • the (C) component may be used alone. Alternatively, two or more of the (C) components may be used in combination.
  • the amine or the amine compound as the (D) component immobilizes copper ions eluted by the flux effect of the (C) component and suppresses the action of a carboxyl group of the fatty acid at room temperature (25° C.).
  • the (D) component preferably contains triethanolamine (TEA, N(CH 2 CH 2 OH) 3 ) or 4,4′-diamino-3,3′-dimethyldiphenylmethane.
  • TEA triethanolamine
  • An example of a commercially available product of 4,4′-diamino-3,3′-dimethyldiphenylmethane may include an amine compound manufactured by Nippon Kayaku Co., Ltd. (product name: Kayahard AA).
  • the (D) component may be used alone. Alternatively, two or more of the (D) components may be used in combination.
  • the content of the (A) component with respect to 100 parts by mass in total of the (A) component and the (B) component is preferably 80 to 98 parts by mass, more preferably 85 to 95 parts by mass, from the viewpoint of the adhesiveness of the resin composition and the specific resistance of the resin composition after curing.
  • the content of the (A) component with respect to 100 parts by mass in total of the (A) component and the (B) component is also preferably 80 to 98 parts by mass, more preferably 85 to 95 parts by mass.
  • the decrease in mass of the resin composition during curing is as low as less than 1%. Therefore, the preferable content of the (A) component in the cured product is similar to the content of the (A) component before curing.
  • quantitative analysis of the (A) component is performed by a thermogravimetric analyzer.
  • the content of the (B) component with respect to 100 parts by mass in total of the (A) component and the (B) component is preferably 2 to 20 parts by mass, more preferably 5 to 15 parts by mass, from the viewpoint of the curing properties of the resin composition and the specific resistance of the resin composition after curing.
  • the content of the (B) component with respect to 100 parts by mass in total of the (A) component and the (B) component is also preferably 2 to 20 parts by mass, more preferably 5 to 15 parts by mass.
  • quantitative analysis of the (B) component is performed by an ion chromatograph-mass spectrometer.
  • the content of the (C) component with respect to 100 parts by mass in total of the (A) component and the (B) component is preferably 1 to 3 parts by mass, more preferably 1 part by mass.
  • the content of the (C) component is less than 1 part by mass, the specific resistance value of the resin composition after curing is likely to become high.
  • the content of the (C) component is more than 3 parts by mass, the pot life of the resin composition is likely to become short.
  • the content of the (C) component with respect to 100 parts by mass in total of the (A) component and the (B) component is also more preferably 1 to 3 parts by mass.
  • quantitative analysis of the (C) component is performed by an ion chromatograph-mass spectrometer.
  • the content of the (D) component with respect to 100 parts by mass in total of the (A) component and the (B) component is preferably 1 to 3 parts by mass, more preferably 3 parts by mass.
  • the content of the (D) component is less than 1 part by mass, the pot life of the resin composition is likely to become short.
  • the content of the (D) component is more than 3 parts by mass, the specific resistance value of the resin composition after curing is likely to become high.
  • the content of the diluent with respect to 100 parts by mass of the resin composition is preferably 10 to 20 parts by mass.
  • the resin composition according to the present invention may further include additives as necessary, for example, a curing accelerator such as imidazole (for instance, 2-phenyl-4-methyl-5-hydroxymethylimidazole manufactured by Shikoku Chemicals Corporation (product name: CUREZOL 2P4MHZ-PW)), a wet dispersant such as carboxylic acid salt (for instance, a dispersant manufactured by Croda International Plc (product name: Hypermer KD-57)), a leveling agent, a coloring agent, an ion trapping agent, an antifoaming agent, and a flame retardant.
  • a curing accelerator such as imidazole (for instance, 2-phenyl-4-methyl-5-hydroxymethylimidazole manufactured by Shikoku Chemicals Corporation (product name: CUREZOL 2P4MHZ-PW)
  • a wet dispersant such as carboxylic acid salt (for instance, a dispersant manufactured by Croda International Plc (product name: Hypermer KD-57)
  • the resin composition according to the present invention can be obtained by, for example, simultaneously or separately stirring, melting, mixing and dispersing the (A) to (D) components, additives, and the like, while performing heat treatment as necessary.
  • An apparatus for these mixing, stirring, dispersing, and the like is not particularly limited. Examples of such an apparatus to be used may include a kneader, a three-roll mill, a ball mill, a planetary mixer, a bead mill, and the like which are equipped with a stirrer and a heater. Also, an appropriate combination of these apparatuses may be used.
  • the initial viscosity of the resin composition is preferably 20 to 25 Pa ⁇ s, from the viewpoint of screen printing properties.
  • the initial viscosity of the resin composition is measured within 24 hours after the resin composition has been prepared, at 25° C. with 10 rotations using a Brookfield-type viscometer (Model No.: HBDV-1, No. 14 rotor).
  • the resin composition according to the present invention is formed or coated on a desired position of an electronic component, such as on the conductive portion of a substrate and the electrode portion of a semiconductor element, by screen printing or a dispenser.
  • the curing condition of the resin composition according to the present invention is preferably 150 to 300° C. for 5 to 30 minutes, particularly suitably high temperature for a short period at 200 to 220° C. for 20 to 40 minutes.
  • a cured product of the resin composition has low specific resistance.
  • the resin composition according to the present invention is suitable for conductive copper pastes, and is suitable as an adhesive for electronic components, such as between the electrode portion of a semiconductor element and the conductive portion of a substrate.
  • the semiconductor device includes a cured product of the above-described resin composition, that is, a cured product of a conductive copper paste.
  • the semiconductor device also includes, for example, a substrate having a conductive portion and a semiconductor element having an electrode portion. The conductive portion of a substrate and the electrode portion of a semiconductor element are connected via a cured film of a resin composition which is a cured product of the above-described resin composition.
  • the semiconductor device according to the present invention has a small connection resistance value between the electrode portion of a semiconductor element and the conductive portion of a substrate. Therefore, the semiconductor device according to the present invention has high reliability.
  • the (A) component an electrolytic copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: ECY-4B large particle size product, oxygen amount: 0.08%, specific surface area: 0.258 m 2 /g, tap density: 3.77 g/cm 3 , average particle size: 10.9 ⁇ m); an electrolytic copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: ECY-4B, oxygen amount: 0.11%, specific surface area: 0.223 m 2 /g, tap density: 4.65 g/cm 3 , average particle size: 6.7 ⁇ m); a liquid phase reduced copper powder manufactured by Mitsui Mining & Smelting Co., Ltd.
  • the (B) component there were used: a bisphenol F-type epoxy resin manufactured by DIC Corporation (product name: EPICLON EXA-835LV); a bisphenol A-type epoxy resin manufactured by Asahi Kasei E-materials Corporation (product name: AER6072); a Novolac-type phenolic resin manufactured by Meiwa Plastic Industries, Ltd. (product name: MEH-8005); a Novolac-type phenolic resin manufactured by Gun Ei Chemical Industry Co., Ltd. (product name: Resitop PSM4324); a resol-type phenolic resin manufactured by Showa Denko K.K.
  • the (C) component there were used oleic acid and stearic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • the (D) component there were used triethanolamine manufactured by Wako Pure Chemical Industries, Ltd. (TEA, 2,2′,2′′-nitrilotriethanol) and amine 4,4′-diamino-3,3′-dimethyldiphenylmethane manufactured by Nippon Kayaku Co., Ltd. (product name: Kayahard AA).
  • Resin compositions were prepared by uniformly mixing and kneading a raw material by a three-roll mill at ratios illustrated in Tables 1 to 5.
  • the (A) component, the (B) component, the (C) component, and the (D) component were uniformly mixed and kneaded by a three-roll mill to prepare a resin composition.
  • the viscosity was measured by a Brookfield-type viscometer (Model No.: HBDV-1, No. 14 rotor, 10 rpm). A diluent was added such that the measured viscosity became 20 to 25 Pa ⁇ s. It is noted that when the (B) component was solid and was difficult to mix and knead, the (B) component was previously dissolved in part of a diluent, and thereafter other components were mixed and kneaded.
  • the resin composition was measured within 24 hours after it has been prepared, at 25° C. with 10 rotations using a Brookfield-type viscometer (HBDV-1, No. 14 rotor).
  • a pattern having a width of 1 mm and a length of 71 mm was printed with the resin composition on an alumina substrate using a screen printer.
  • the printed resin composition was subjected to heat treatment in a nitrogen atmosphere at 200° C. ⁇ 30 minutes by a belt conveyor curing oven so that it was cured.
  • the thickness of the obtained cured film of the resin composition was measured using a surface texture and shape measuring instrument manufactured by Tokyo Seimitsu Co., Ltd. (Model No.: Surfcom 1500SD-2).
  • the resistance value was measured using a digital multimeter manufactured by TFF Keithley Instruments, Inc. (Model No.: 2001).
  • the volume resistivity was calculated as the specific resistance value.
  • the specific resistance after curing is low regardless of the type of the thermosetting resin, and furthermore, does not significantly change after curing depending on the content of the copper powder. Therefore, the resin composition according to the present invention is extraordinarily useful as a conductive copper paste.

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Abstract

An object of the present invention is to provide: a resin composition in which the specific resistance after curing is low regardless of the type of a thermosetting resin, and furthermore, the specific resistance after curing does not significantly change depending on the content of a copper powder; and a conductive copper paste including the resin composition. There are provided a resin composition including (A) a copper powder having an oxygen content of 0.3% by mass or less, (B) a thermosetting resin, (C) a fatty acid, and (D) an amine or an amine compound, as well as a conductive copper paste containing the resin composition. The (A) component has an average particle size of preferably 1 to 10 μm.

Description

TECHNICAL FIELD
The present invention relates to a resin composition, a conductive copper paste, and a semiconductor device. In particular, the present invention relates to a resin composition, a conductive copper paste, and a semiconductor device, which have low specific resistance.
BACKGROUND ART
A semiconductor device in which the electrode portion of a semiconductor element and the conductive portion of a substrate are bonded to each other is very extensively used. For bonding the electrode portion of a semiconductor element and the conductive portion of a substrate, a conductive adhesive or soldering is used. The conductive adhesive has the advantage that bonding can be performed at a lower temperature than soldering. However, the specific resistance of the conductive adhesive is higher than that of solder. Therefore, studies are underway to reduce the resistance of the conductive adhesive.
Known conductive adhesives include silver as a conductive filler. However, since silver has migration properties and has increased in price, studies are underway to use copper as a conductive filler. The conductive adhesive including copper generally has the drawback that the specific resistance is high.
As a paste including copper as a conductive filler, there is disclosed a conductive copper paste containing as essential components a copper powder having a predetermined particle size distribution and tap density, a thermosetting resin, an organic carboxylic acid, and a chelate agent, and furthermore, polybutadiene (claim 1 and paragraphs 0013 and 0022 of PATENT LITERATURE 1).
This conductive copper paste is prepared such that it is a conductive copper paste which enables screen printing, has favorable conductivity comparable to a conductive silver paste, and possesses migration resistance properties, and which is suitable for through holes corresponding to fine pitches (paragraph 0008 of PATENT LITERATURE 1). It is disclosed that specific examples of the organic carboxylic acid may include salicylic acid, benzoic acid, tartaric acid, citric acid, maleic acid, succinic acid, fumaric acid, and malonic acid (paragraph 0018 of PATENT LITERATURE 1). All these organic carboxylic acids are solid at normal temperature.
Also, there is disclosed a conductive paste for circuit boards which includes a copper-containing metal powder, a compound containing at least two (meth) acryl groups, and a β-dicarbonyl compound, and which does not substantially contain an azo compound and a peroxide (claim 1 of PATENT LITERATURE 2). It is described that this conductive paste for circuit boards may include a compound having flux activity (paragraph 0014 of PATENT LITERATURE 2). An example of the compound having flux activity may include aliphatic carboxylic acids such as oleic acid (paragraphs 0038 and 0046 of PATENT LITERATURE 2).
Furthermore, there is disclosed a conductive copper paste composition which includes a prepolymer having at least two hydroxyl groups and at least one tertiary amine in one molecule, a copper powder, an amino resin, and a reducing agent, and which can be etched by an acidic etchant (claim 1 of PATENT LITERATURE 3). It is disclosed that an example of the reducing agent may include an unsaturated monocarboxylic acid having 12 to 23 carbon atoms, such as oleic acid and linoleic acid (paragraph 0016 of PATENT LITERATURE 3).
However, it is known that these conductive copper pastes have the following problems. That is, the specific resistance of the conductive copper pastes is likely to become high, and furthermore, significantly changes after curing depending on the content of a copper powder. Moreover, since usable resins are substantially limited (a resol-type phenolic resin according to PATENT LITERATURE 1, a compound having at least two (meth)acryl groups in one molecular according to PATENT LITERATURE 2, and a prepolymer having at least two hydroxyl groups and at least one tertiary amine in one molecule and an amino resin according to PATENT LITERATURE 3), applicable uses are limited.
CITATION LIST Patent Literature
PATENT LITERATURE 1: JP-A-2008-130301
PATENT LITERATURE 2: JP-A-2009-295895
PATENT LITERATURE 3: JP-A-10-064333
SUMMARY OF THE INVENTION Problems to be Solved by the Invention
The present inventors intensively conducted studies, and found that when a specific copper powder, a thermosetting resin, a fatty acid, and an amine or an amine compound are used in combination, there can be provided: a resin composition in which the specific resistance is low regardless of the type of the thermosetting resin, and the specific resistance of the conductive copper paste after curing does not significantly change depending on the content of the copper powder; and a conductive copper paste including the resin composition. That is, an object of the present invention is to provide: a resin composition in which the specific resistance after curing is low regardless of the type of a thermosetting resin and does not significantly change depending on the content of a copper powder; and a conductive copper paste including the resin composition.
Solution to the Problems
The present invention relates to a resin composition, a conductive copper paste, a cured product of a conductive copper paste, and a semiconductor device, which have solved the above-described problems by having the following configurations.
<1> A resin composition including (A) a copper powder having an oxygen content of 0.3% by mass or less, (B) a thermosetting resin, (C) a fatty acid, and (D) an amine or an amine compound.
<2> The resin composition according to the above-described <1>, in which the (A) component has an average particle size of 1 to 10 μm.
<3> The resin composition according to the above-described <1>, in which the (B) component is at least one selected from the group consisting of an epoxy resin, a phenolic resin, a melamine resin, a xylene resin, and a urea resin.
<4> The resin composition according to the above-described <1>, in which the (C) component is at least one selected from the group consisting of oleic acid, linoleic acid, linolenic acid, stearic acid, palmitic acid, and lauric acid.
<5> The resin composition according to the above-described <1>, in which the (D) component contains triethanolamine or 4,4′-diamino-3,3′-dimethyldiphenylmethane.
<6> A conductive copper paste including the resin composition according to the above-described <1>.
<7> A cured product of the conductive copper paste according to the above-described <6>.
<8> A semiconductor device including a cured product of the resin composition according to the above-described <1>.
Effects of the Invention
According to the present invention <1>, there can be provided a resin composition in which the specific resistance is low after curing regardless of the type of the thermosetting resin and does not significantly change after curing depending on the content of the copper powder (the specific resistance value is less than 1×10−4 Ω·cm).
According to the present invention <6>, there can be provided a conductive copper paste including the resin composition in which the specific resistance is low after curing regardless of the type of the thermosetting resin and does not significantly change after curing depending on the content of the copper powder (the specific resistance value is less than 1×10−4 Ω·cm). According to the invention <7>, there can be provided a cured product of a low-resistance conductive copper paste for obtaining a highly reliable semiconductor device. According to the invention <8>, there can be obtained a highly reliable semiconductor device which, for example, has a small connection resistance value between the electrode portion of a semiconductor element and the conductive portion of a substrate.
DESCRIPTION OF THE EMBODIMENTS
<Resin Composition>
The resin composition according to the present invention (hereinafter, referred to as the resin composition) includes (A) a copper powder having an oxygen content of 0.3% by mass or less, (B) a thermosetting resin, (C) a fatty acid, and (D) an amine or an amine compound.
The copper powder having an oxygen content of 0.3% by mass or less relative to 100% of the copper powder as the (A) component imparts conductivity to the resin composition after curing. The resin composition is advantageous in that the specific resistance after curing does not significantly change depending on the content of the (A) component. Here, the oxygen content of the copper powder is measured by hydrogen loss method. Specifically, an oxygen-nitrogen analyzer (Model: EMGA-623W) manufactured by Horiba, Ltd. is used for the measurement. It is noted that the oxygen content of the copper powder in the resin composition is measured after the copper powder is retrieved from the resin composition by solvent. Also, the (A) component preferably has an average particle size of 1 to 10 μm, from the viewpoint of the oxygen content and the specific resistance of the resin composition after curing. An example of the (A) component may include a copper powder having a rod-like, flake-like, or spherical shape. A more preferable example of the (A) component may be a rod-like copper powder obtained by crushing a particle-shaped dendritic copper powder (electrolytic copper powder). Also, it is preferable that the tap density of the (A) component is high from the viewpoint of the specific resistance of the resin composition after curing. Examples of a commercially available product of the (A) component may include: an electrolytic copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (ECY-4B, oxygen amount: 0.11%, specific surface area: 0.223 m2/g, tap density: 4.65 g/cm3, average particle size: 6.7 μm); an electrolytic copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: ECY-4B large particle size product, oxygen amount: 0.08%, specific surface area: 0.258 m2/g, tap density: 3.77 g/cm3, average particle size: 10.9 μm); a liquid phase reduced copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: CS-20D, oxygen amount: 0.27%, specific surface area: 0.339 m2/g, tap density: 3.85 g/cm3, average particle size: 2.9 μm); and a liquid phase reduced copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: CS-10D, oxygen amount: 0.26%, specific surface area: 0.656 m2/g, tap density: 4.55 g/cm3, average particle size: 1.0 μm). The copper powder (ECY-4B) manufactured by Mitsui Mining & Smelting Co., Ltd. and the electrolytic copper powder (product name: ECY-4B large particle size product) manufactured by Mitsui Mining & Smelting Co., Ltd., which have a low oxygen content, are preferable. Here, measurement is performed for the specific surface area by BET method, for the tap density by a shaking specific gravity measuring device (tap machine), and for the average particle size by a laser diffraction scattering particle distribution measuring device. The (A) component may be used alone. Alternatively, two or more of the (A) components may be used in combination.
The thermosetting resin as the (B) component imparts adhesiveness and curing properties to the resin composition. In the resin composition, the specific resistance of the resin composition after curing can be lowered regardless of the type of the thermosetting resin. The (B) component is preferably, but not particularly limited to, at least one selected from the group consisting of an epoxy resin, a phenolic resin, a melamine resin, a xylene resin, and a urea resin, from the viewpoint of adhesive strength. Examples of a commercially available product of the (B) component may include: a bisphenol F-type epoxy resin manufactured by DIC Corporation (product name: EPICLON EXA-835LV); a bisphenol A-type epoxy resin manufactured by Asahi Kasei E-materials Corporation (product name: AER6072); a Novolac-type phenolic resin manufactured by Meiwa Plastic Industries, Ltd. (product name: MEH-8005); a Novolac-type phenolic resin manufactured by Gun Ei Chemical Industry Co., Ltd. (product name: Resitop PSM4324); a resol-type phenolic resin manufactured by Showa Highpolymer Co., Ltd. (product name: Shonol CKM-908); and a resol-type phenolic resin manufactured by Showa Highpolymer Co., Ltd. (product name: Shonol CKM-918A). The (B) component may be used alone. Alternatively, two or more of the (B) components may be used in combination. It is noted that solid resin such as a resol-type phenolic resin may be heated and mixed with the later-described diluent when preparing a paste so that it is used in a liquid state.
The (C) component functions as a flux component which allows an oxidized layer on the surface of the copper powder to be eluted. The (C) component is preferably at least one selected from the group consisting of
oleic acid (CH3(CH2)7CH═CH(CH2)7COOH, cis-9-octadecenoic acid, liquid),
linoleic acid (CH3—(CH2)4—CH═CHCH2CH═CH(CH2)7COOH, cis-9,
cis-12-octadecadienoic acid, liquid),
linolenic acid (CH3CH2CH═CHCH2CH═CHCH2CH═CH(CH2)7COOH, cis-9, cis-12,
cis-15-octadecatrienoic acid, liquid),
stearic acid (CH3(CH2)16COOH, octadecanoic acid, white solid),
palmitic acid (CH3(CH2)14COOH, hexadecanoic acid, white solid), and
lauric acid (CH3(CH2)10COOH, dodecanoic acid, white solid),
from the viewpoint of excellent wettability with the copper powder. Oleic acid is more preferable. The (C) component may be used alone. Alternatively, two or more of the (C) components may be used in combination.
The amine or the amine compound as the (D) component immobilizes copper ions eluted by the flux effect of the (C) component and suppresses the action of a carboxyl group of the fatty acid at room temperature (25° C.). The (D) component preferably contains triethanolamine (TEA, N(CH2CH2OH)3) or 4,4′-diamino-3,3′-dimethyldiphenylmethane. An example of a commercially available product of 4,4′-diamino-3,3′-dimethyldiphenylmethane may include an amine compound manufactured by Nippon Kayaku Co., Ltd. (product name: Kayahard AA). The (D) component may be used alone. Alternatively, two or more of the (D) components may be used in combination.
The content of the (A) component with respect to 100 parts by mass in total of the (A) component and the (B) component is preferably 80 to 98 parts by mass, more preferably 85 to 95 parts by mass, from the viewpoint of the adhesiveness of the resin composition and the specific resistance of the resin composition after curing.
In a cured product of the resin composition, the content of the (A) component with respect to 100 parts by mass in total of the (A) component and the (B) component is also preferably 80 to 98 parts by mass, more preferably 85 to 95 parts by mass. Here, the decrease in mass of the resin composition during curing is as low as less than 1%. Therefore, the preferable content of the (A) component in the cured product is similar to the content of the (A) component before curing. Here, quantitative analysis of the (A) component is performed by a thermogravimetric analyzer.
The content of the (B) component with respect to 100 parts by mass in total of the (A) component and the (B) component is preferably 2 to 20 parts by mass, more preferably 5 to 15 parts by mass, from the viewpoint of the curing properties of the resin composition and the specific resistance of the resin composition after curing.
In a cured product of the resin composition, the content of the (B) component with respect to 100 parts by mass in total of the (A) component and the (B) component is also preferably 2 to 20 parts by mass, more preferably 5 to 15 parts by mass. Here, quantitative analysis of the (B) component is performed by an ion chromatograph-mass spectrometer.
The content of the (C) component with respect to 100 parts by mass in total of the (A) component and the (B) component is preferably 1 to 3 parts by mass, more preferably 1 part by mass. When the content of the (C) component is less than 1 part by mass, the specific resistance value of the resin composition after curing is likely to become high. When the content of the (C) component is more than 3 parts by mass, the pot life of the resin composition is likely to become short.
In a cured product of the resin composition, the content of the (C) component with respect to 100 parts by mass in total of the (A) component and the (B) component is also more preferably 1 to 3 parts by mass. Here, quantitative analysis of the (C) component is performed by an ion chromatograph-mass spectrometer.
The content of the (D) component with respect to 100 parts by mass in total of the (A) component and the (B) component is preferably 1 to 3 parts by mass, more preferably 3 parts by mass. When the content of the (D) component is less than 1 part by mass, the pot life of the resin composition is likely to become short. When the content of the (D) component is more than 3 parts by mass, the specific resistance value of the resin composition after curing is likely to become high.
The resin composition may further include a diluent, from the viewpoint of melting or liquefaction when the (B) component is solid, and preparation of the viscosity of the resin composition. The diluent can be appropriately selected in consideration of the solubility and curing condition of the thermosetting resin. Specific examples of the diluent may include ethyl carbitol, ethyl carbitol acetate, butyl carbitol, butyl carbitol acetate, terpineol, dihydroterpineol, ethyl cellosolve, butyl cellosolve, ethyl cellosolve acetate, butyl cellosolve acetate, and phenoxyethanol. From the viewpoint of the drying properties of the resin composition, phenoxyethanol manufactured by Toho Chemical Industry Co., Ltd. (product name: HISOLV EPH) is preferably used.
The content of the diluent with respect to 100 parts by mass of the resin composition is preferably 10 to 20 parts by mass.
As long as the object of the present invention is not impaired, the resin composition according to the present invention may further include additives as necessary, for example, a curing accelerator such as imidazole (for instance, 2-phenyl-4-methyl-5-hydroxymethylimidazole manufactured by Shikoku Chemicals Corporation (product name: CUREZOL 2P4MHZ-PW)), a wet dispersant such as carboxylic acid salt (for instance, a dispersant manufactured by Croda International Plc (product name: Hypermer KD-57)), a leveling agent, a coloring agent, an ion trapping agent, an antifoaming agent, and a flame retardant.
The resin composition according to the present invention can be obtained by, for example, simultaneously or separately stirring, melting, mixing and dispersing the (A) to (D) components, additives, and the like, while performing heat treatment as necessary. An apparatus for these mixing, stirring, dispersing, and the like is not particularly limited. Examples of such an apparatus to be used may include a kneader, a three-roll mill, a ball mill, a planetary mixer, a bead mill, and the like which are equipped with a stirrer and a heater. Also, an appropriate combination of these apparatuses may be used.
The initial viscosity of the resin composition is preferably 20 to 25 Pa·s, from the viewpoint of screen printing properties. Here, the initial viscosity of the resin composition is measured within 24 hours after the resin composition has been prepared, at 25° C. with 10 rotations using a Brookfield-type viscometer (Model No.: HBDV-1, No. 14 rotor).
The resin composition according to the present invention is formed or coated on a desired position of an electronic component, such as on the conductive portion of a substrate and the electrode portion of a semiconductor element, by screen printing or a dispenser.
The curing condition of the resin composition according to the present invention is preferably 150 to 300° C. for 5 to 30 minutes, particularly suitably high temperature for a short period at 200 to 220° C. for 20 to 40 minutes. A cured product of the resin composition has low specific resistance.
The resin composition according to the present invention is suitable for conductive copper pastes, and is suitable as an adhesive for electronic components, such as between the electrode portion of a semiconductor element and the conductive portion of a substrate.
<Semiconductor Device>
The semiconductor device according to the present invention includes a cured product of the above-described resin composition, that is, a cured product of a conductive copper paste. The semiconductor device also includes, for example, a substrate having a conductive portion and a semiconductor element having an electrode portion. The conductive portion of a substrate and the electrode portion of a semiconductor element are connected via a cured film of a resin composition which is a cured product of the above-described resin composition.
The semiconductor device according to the present invention has a small connection resistance value between the electrode portion of a semiconductor element and the conductive portion of a substrate. Therefore, the semiconductor device according to the present invention has high reliability.
EXAMPLES
The present invention will be described by way of examples. However, the present invention is not limited to these examples. It is noted that in the following examples, parts and % indicate parts by mass and % by mass respectively, unless otherwise stated.
In Examples and Comparative Examples,
there were used as the (A) component: an electrolytic copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: ECY-4B large particle size product, oxygen amount: 0.08%, specific surface area: 0.258 m2/g, tap density: 3.77 g/cm3, average particle size: 10.9 μm); an electrolytic copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: ECY-4B, oxygen amount: 0.11%, specific surface area: 0.223 m2/g, tap density: 4.65 g/cm3, average particle size: 6.7 μm); a liquid phase reduced copper powder manufactured by Mitsui Mining & Smelting Co., Ltd.
(product name: CS-20D, oxygen amount: 0.27%, specific surface area: 0.339 m2/g, tap density: 3.85 g/cm3, average particle size: 2.9 μm); and a liquid phase reduced copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: CS-10D, oxygen amount: 0.26%, specific surface area: 0.656 m2/g, tap density: 4.55 g/cm3, average particle size: 1.0 μm). It is noted that there was also used the (A) component having an oxygen amount of 0.21%, a specific surface area of 0.252 m2/g, and a tap density of 4.44 g/cm3 obtained by oxidizing an electrolytic copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: ECY-4B) in the atmosphere at 100° C. for 15 hours. Furthermore, there was also used the (A) component having an oxygen amount of 0.47%, a specific surface area of 0.446 m2/g, and a tap density of 4.08 g/cm3 obtained by oxidizing an electrolytic copper powder manufactured by Mitsui Mining & Smelting Co., Ltd. (product name: ECY-4B) in the atmosphere at 100° C. for 550 hours.
As the (B) component, there were used: a bisphenol F-type epoxy resin manufactured by DIC Corporation (product name: EPICLON EXA-835LV); a bisphenol A-type epoxy resin manufactured by Asahi Kasei E-materials Corporation (product name: AER6072); a Novolac-type phenolic resin manufactured by Meiwa Plastic Industries, Ltd. (product name: MEH-8005); a Novolac-type phenolic resin manufactured by Gun Ei Chemical Industry Co., Ltd. (product name: Resitop PSM4324); a resol-type phenolic resin manufactured by Showa Denko K.K. (product name: Shonol CKM-908); and a resol-type phenolic resin manufactured by Showa Denko K.K. (product name: Shonol CKM-918A).
As the (C) component, there were used oleic acid and stearic acid manufactured by Wako Pure Chemical Industries, Ltd.
As the (D) component, there were used triethanolamine manufactured by Wako Pure Chemical Industries, Ltd. (TEA, 2,2′,2″-nitrilotriethanol) and amine 4,4′-diamino-3,3′-dimethyldiphenylmethane manufactured by Nippon Kayaku Co., Ltd. (product name: Kayahard AA).
There were used: imidazole manufactured by Shikoku Chemicals Corporation (2-phenyl-4-methyl-5-hydroxymethylimidazole, product name: CUREZOL 2P4MHZ-PW) as a curing accelerator; a dispersant manufactured by Croda International Plc. (product name: Hypermer KD-57) as a dispersant; and a diluent manufactured by Toho Chemical Industry Co., Ltd. (product name: HISOLV EPH) as a diluent.
Examples 1 to 30, Comparative Examples 1 to 8
Resin compositions were prepared by uniformly mixing and kneading a raw material by a three-roll mill at ratios illustrated in Tables 1 to 5. The (A) component, the (B) component, the (C) component, and the (D) component were uniformly mixed and kneaded by a three-roll mill to prepare a resin composition. Lastly, the viscosity was measured by a Brookfield-type viscometer (Model No.: HBDV-1, No. 14 rotor, 10 rpm). A diluent was added such that the measured viscosity became 20 to 25 Pa·s. It is noted that when the (B) component was solid and was difficult to mix and knead, the (B) component was previously dissolved in part of a diluent, and thereafter other components were mixed and kneaded.
<Evaluation Method>
<<Measurement of Initial Viscosity>>
The resin composition was measured within 24 hours after it has been prepared, at 25° C. with 10 rotations using a Brookfield-type viscometer (HBDV-1, No. 14 rotor).
<<Measurement of Specific Resistance Value>>
A pattern having a width of 1 mm and a length of 71 mm was printed with the resin composition on an alumina substrate using a screen printer. The printed resin composition was subjected to heat treatment in a nitrogen atmosphere at 200° C.×30 minutes by a belt conveyor curing oven so that it was cured. The thickness of the obtained cured film of the resin composition was measured using a surface texture and shape measuring instrument manufactured by Tokyo Seimitsu Co., Ltd. (Model No.: Surfcom 1500SD-2). The resistance value was measured using a digital multimeter manufactured by TFF Keithley Instruments, Inc. (Model No.: 2001). The volume resistivity was calculated as the specific resistance value.
TABLE 1
Com- Com- Com- Com- Com-
Exam- Exam- Exam- Exam- Exam- parative parative parative parative parative
ple ple ple ple ple Example Example Example Example Example
1 2 3 4 5 1 2 3 4 5
(A) Cu ECY- O2:0.1% 87.5 90.0 92.5 95.0 0 0 0 0 0 0
powder 4B O2:0.2% 0 0 0 0 90.0 0 0 0 0 0
O2:0.47% 0 0 0 0 0 85.0 87.5 90.0 92.5 95.0
(B) CKM 918A 12.5 10.0 7.5 5.0 10.0 15.0 12.5 10.0 7.5 5.0
Resol-
type
phenol
(C) Oleic acid 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Fatty
acid
(D) TEA 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
Amine
Diluent EPH 16.7 16.3 13.0 15.7 15.8 21.0 18.5 15.0 13.5 11.2
Viscosity measured at 10 23 25 24 24 25 23 21 25 22 25
rpm (Pa · s))
Specific resistance value 76 59 72 58 117 Measure- Measure- Measure- Measure- Measure-
(μΩ · cm) after curing at ment ment ment ment ment
200° C. × 30 min (N2) disabled disabled disabled disabled disabled
TABLE 2
Example Example Example Example Example Example Example Example Example
6 7 8 9 10 11 12 13 14
(A) Cu ECY-4B 85.0 87.5 90.0 92.5 95.0 0 0 0 0
powder Large
particle
size
product
(O2:
0.08%)
ECY-4B 0 0 0 0 0 87.5 90.0 92.5 95.0
(O2:
0.03%)
(B) CKM 15.0 12.5 10.0 7.5 5.0 12.5 10.0 7.7 5.0
Resol- 918A
type
phenolic
resin
(C) Fatty Oleic 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
acid acid
(D) TEA 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
Amine
Diluent EPH 19.0 16.7 16.3 13.0 15.7 16.7 16.3 13.0 15.7
Viscosity (measured 25 25 20 23 20 23 25 24 24
at 10 rpm (Pa · s))
Specific resistance 61 56 49 62 50 76 59 72 58
value (μΩ · cm) after
curing at 200° C. × 30
min (N2)
TABLE 3
Example Example Example Example Example Example Example Example Example Example
15 16 17 18 19 20 21 22 23 24
(A) Cu CS-20D 85.0 87.5 90.0 92.5 95.0 0 0 0 0 0
powder (O2:
0.27%)
CS-10D 0 0 0 0 0 85.0 87.5 90.0 92.5 95.0
(O2:
0.26%)
(B) Resol-type CKM 15.0 12.5 10.0 7.7 5.0 15.0 2.5 10.0 7.5 5.0
phenolic resin 918A
(C) Fatty acid Oleic 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
acid
(D) Amine TEA 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
Diluent EPH 19.0 18.7 15.8 15.0 11.7 19.0 17.5 15.8 14.3 12.7
Viscosity (measured at 10 22 23 24 22 22 23 24 24 23 24
rpm (Pa · s))
Specific resistance value 109 56 30 23 42 40 26 16 18 30
(μΩ · cm) after curing at
200° C. × 30 min (N2)
TABLE 4
Exam- Exam- Exam- Exam-
ple 2 ple 25 ple 26 ple 27
(A) Cu powder ECY-4B 90.0 90.0 90.0 90.0
(B) Bis F-type EXA835LV 0 5.0 5.5 0
Com- epoxy resin
ponent Bis A-type AER6072 0 0 0 8.1
epoxy resin
Novolac-type MEH8005 0 0 4.5 0
phenol PSM4324 0 0 0 1.9
Resol-type CKM908 0 5.0 0 0
phenol CKM918A 10.0 0 0 0
(C) Fatty acid Oleic acid 1.0 0 0 0
Stearic acid 0 1.0 1.0 1.0
(D) Component TEA 3.0 0 3.0 3.0
Kayahard AA 0 1.5 0 0
Curing accelerator 2P4MHZ 0 0.3 0.3 0.3
Dispersant Hypermer 0 0.5 0.5 0.5
KD-57
Diluent EPH 16.3 8.9 8.0 20.2
Viscosity (measured 25 23 20 14
at 10 rpm (Pa · s))
Specific resistance 59 111 116 98
value (μΩ · cm) after
curing at 200° C. × 30 min (N2)
TABLE 5
Com- Com- Com- Ex- Ex- Ex-
parative parative parative am- am- am-
Exam- Exam- Exam- ple ple ple
ple 6 ple 7 ple 8 28 29 30
(A) Cu ECY-4B 90.0 90.0 90.0 90.0 90.0 90.0
powder
(B) CKM 10.00 10.0 10.0 10.0 10.0 10.0
Resol-type 918A
phenolic
resin
(C) Fatty Oleic acid 0 1.0 0 3.0 3.0 1.0
acid
(D)Amine TEA 0 0 3.0 3.0 3.0 1.0
Diluent EPH 6.5 6.5 7.0 7.0 6.5 7.0
Viscosity (measured 21 25 20 25 20 24
at 10 rpm (Pa · s))
Specific resistance 2722 636 1258 59 34 123
value (μΩ · cm) after
curing at 200° C. × 30
min (N2)
As understood from Tables 1 to 3, in all of Examples 1 to 24, the specific resistance value of the resin composition after curing was less than 1×104 Ω·cm. On the contrary, in all of Comparative Examples 1 to 5 in which a copper powder having a high oxygen content was used, the specific resistance value of the resin composition after curing was high.
As understood from Examples 2 and 25 to 26 in Table 4, the specific resistance values of all the resin compositions after curing were less than 1×104 Ω·cm even when the (B) component, the (C) component, or the (D) component was varied.
As understood from Table 5, the specific resistance values of the resin compositions after curing in Examples 28 to 30 were less than 1×104 Ω·cm. On the contrary, in all of Comparative Example 6 without the (C) component and the (D) component, Comparative Example 7 without the (D) component, and Comparative Example 8 without the (C) component, the specific resistance value of the resin composition after curing was high.
As described above, according to the resin composition according to the present invention, the specific resistance after curing is low regardless of the type of the thermosetting resin, and furthermore, does not significantly change after curing depending on the content of the copper powder. Therefore, the resin composition according to the present invention is extraordinarily useful as a conductive copper paste.

Claims (7)

The invention claimed is:
1. A resin composition, comprising:
(A) a copper powder having an oxygen content of 0.3% by mass or less;
(B) a thermosetting resin;
(C) a fatty acid; and
(D) an amine or an amine compound,
wherein the (B) component is at least one selected from the group consisting of an epoxy resin, a Novolac-type phenolic resin, a melamine resin, a xylene resin, and a urea resin.
2. The resin composition according to claim 1,
wherein the (A) component has an average particle size of 1 to 10 μm.
3. The resin composition according to claim 1,
wherein the (C) component is at least one selected from the group consisting of oleic acid, linoleic acid, linolenic acid, stearic acid, palmitic acid, and lauric acid.
4. The resin composition according to claim 1,
wherein the (D) component includes triethanolamine or 4,4′-diamino-3,3′-dimethyldiphenylmethane.
5. A conductive copper paste comprising the resin composition according to claim 1.
6. A cured product of the conductive copper paste according to claim 5.
7. A semiconductor device containing a cured product of the resin composition according to claim 1.
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JP2017141330A (en) * 2016-02-08 2017-08-17 ナミックス株式会社 Resin composition, conductive copper paste, cured product of conductive copper paste, and semiconductor device
JP6948111B2 (en) * 2016-02-09 2021-10-13 ナミックス株式会社 Resin compositions, conductive copper pastes, and semiconductor devices
CN112399896B (en) * 2018-06-26 2023-06-09 阿尔法装配解决方案公司 Nano copper paste and film for sintered die attach and similar applications
CN111205600B (en) * 2020-02-21 2023-04-21 中国石油化工股份有限公司 Epoxy resin preparation, filler, pipeline repairing material and preparation method
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